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Exchange operator

In quantum mechanics, the exchange operator, often denoted as \hat{P}_{12} for two particles, is a permutation operator that interchanges the labels of identical particles within a multi-particle wave function, thereby classifying the symmetry under particle exchange as a fundamental property of quantum states.^[1] This operator acts on unphysical labels in one-particle wave functions to ensure that physical solutions are proper eigenfunctions, with eigenvalues of +1 for symmetric states or -1 for antisymmetric states.^[1] The exchange operator is central to the treatment of indistinguishable particles, where the Hamiltonian of the system must commute with it to allow common eigenfunctions that respect particle statistics.^[1] For bosons, the eigenvalue +1 corresponds to fully symmetric wave functions, permitting multiple particles to occupy the same quantum state and leading to phenomena like Bose-Einstein condensation.^[1]^[2] In contrast, for fermions, the eigenvalue -1 enforces antisymmetric wave functions, which directly underpin Pauli's exclusion principle by making it impossible for two fermions to share identical quantum states, such as in atomic orbitals.^[1] Mathematically, for a two-particle system, the action of the exchange operator on a wave function \psi(1,2) yields \hat{P}_{12} \psi(1,2) = \psi(2,1), where the labels 1 and 2 denote particle coordinates or states.^[1] This formalism extends to systems with more particles via successive pairwise exchanges and is essential for constructing proper multi-particle states in Fock space, influencing applications from molecular spectroscopy to quantum computing.^[3]^[4] The operator's properties also connect to broader exchange interactions in condensed matter physics, where they govern electron correlations and magnetic ordering in materials.^[4]

Fundamentals

Definition

In quantum mechanics, the exchange operator is a linear operator that interchanges the labels of two identical particles within a multi-particle quantum state, ensuring the proper treatment of particle indistinguishability.^[5] This operator, often denoted as \hat{P}_{ij} for particles i and j, acts on the wavefunction by swapping the coordinates or momenta associated with those particles.^[6] For a two-particle system in position space, the action of the exchange operator is explicitly \hat{P}_{12} \psi(\mathbf{r}_1, \mathbf{r}_2) = \psi(\mathbf{r}_2, \mathbf{r}_1), where \psi is the joint wavefunction and \mathbf{r}_1, \mathbf{r}_2 are the position vectors of the particles./09%3A_Indistinguishable_Particles_and_Exchange/9.02%3A_The_exchange_operator_and_Paulis_exclusion_principle) An analogous form applies in momentum space, swapping the momentum labels while preserving the overall state structure./09%3A_Indistinguishable_Particles_and_Exchange/9.02%3A_The_exchange_operator_and_Paulis_exclusion_principle) The exchange operator represents a transposition, a basic permutation in the symmetric group of particle labelings. Permutation operators, including the exchange operator, enforce the required symmetry of the total wavefunction for identical particles: symmetric under even permutations (including the identity) for bosons and antisymmetric under odd permutations (such as a single exchange) for fermions./09%3A_Indistinguishable_Particles_and_Exchange/9.02%3A_The_exchange_operator_and_Paulis_exclusion_principle) Consequently, the eigenvalues of the exchange operator are +1 for bosonic states, yielding symmetric wavefunctions, and -1 for fermionic states, yielding antisymmetric wavefunctions./09%3A_Indistinguishable_Particles_and_Exchange/9.02%3A_The_exchange_operator_and_Paulis_exclusion_principle) The historical origin of the exchange operator traces to the principle of indistinguishability of identical particles, first formalized by Werner Heisenberg in 1926 during his analysis of the helium atom, where he introduced symmetric and antisymmetric combinations of electron states to account for their identical nature.^[7] Paul Dirac independently advanced this framework in the same year, emphasizing antisymmetric wavefunctions for particles obeying the exclusion principle, such as electrons.^[8] These developments laid the foundation for handling multi-particle systems in quantum theory.^[9]

Exchange Symmetry for Identical Particles

In quantum mechanics, identical particles require that the total wavefunction of a multi-particle system exhibit definite symmetry properties under particle exchange to account for their indistinguishability.^[8] This symmetrization postulate, introduced by Dirac, stipulates that the wavefunction must be either totally symmetric or totally antisymmetric with respect to interchange of any two identical particles, depending on the particle's intrinsic nature.^[8] For bosons, which have integer spin, the total wavefunction is symmetric under exchange, corresponding to an exchange eigenvalue of +1; this allows multiple bosons to occupy the same quantum state, leading to phenomena like Bose-Einstein condensation. In contrast, for fermions with half-integer spin, such as electrons, the wavefunction is antisymmetric under exchange, with an eigenvalue of -1, as required by the Pauli exclusion principle, which prohibits two fermions from sharing the identical quantum state. In multi-particle systems, this symmetry enforcement has profound consequences, particularly for fermions, where the wavefunction must be constructed as an antisymmetrized product of single-particle states to eliminate unphysical configurations that would violate the exclusion principle.^[8] For instance, in a two-electron system like the helium atom ground state, the spin part is a symmetric triplet (parallel spins) paired with an antisymmetric spatial wavefunction, while the antisymmetric spin singlet (antiparallel spins) requires a symmetric spatial wavefunction to ensure overall antisymmetry. This exchange symmetry underpins quantum statistics: symmetric wavefunctions lead to Bose-Einstein statistics for bosons, while antisymmetric ones yield Fermi-Dirac statistics for fermions, governing distribution functions in thermal equilibrium. The exchange operator serves as the generator of permutations within the symmetric group, dictating the allowed irreducible representations for the system's Hilbert space based on particle type.^[8]

Mathematical Formulation

Operator Action on Wavefunctions

The exchange operator, often denoted as \hat{P}_{ij} for particles i and j, acts on the wavefunction of a system of identical particles by interchanging their labels, enforcing the symmetry requirements dictated by quantum statistics. For a two-particle product state in the tensor product space, the action is given by

\hat{P}_{ij} \left( |\psi_i\rangle \otimes |\psi_j\rangle \right) = |\psi_j\rangle \otimes |\psi_i\rangle,

where |\psi_i\rangle and |\psi_j\rangle are single-particle states. This transposition operator is unitary and Hermitian, satisfying \hat{P}_{ij}^\dagger = \hat{P}_{ij} and \hat{P}_{ij}^2 = \hat{1}, ensuring it preserves the norm and inner products of the states.^[10] In the position representation, the action of the exchange operator on spatial wavefunctions becomes explicit through coordinate swapping. For a two-particle wavefunction \psi(\mathbf{r}_1, \mathbf{r}_2), the operator yields \hat{P}_{12} \psi(\mathbf{r}_1, \mathbf{r}_2) = \psi(\mathbf{r}_2, \mathbf{r}_1). When particles possess spin, the operator also interchanges spin labels, so for a state \Psi_{m_1 m_2}(\mathbf{r}_1, \mathbf{r}_2), it produces \hat{P}_{12} \Psi_{m_1 m_2}(\mathbf{r}_1, \mathbf{r}_2) = \Psi_{m_2 m_1}(\mathbf{r}_2, \mathbf{r}_1). For multi-particle systems, the exchange operator extends via the symmetric group of permutations, generating all possible label rearrangements. The complete antisymmetrizer for N fermions, essential for constructing Slater determinants, is

\hat{A} = \frac{1}{N!} \sum_P (-1)^p \hat{P},

where the sum runs over all N! permutations P, p denotes the permutation parity (even or odd), and \hat{P} applies the corresponding label swap to the product wavefunction. Applying \hat{A} to an unsymmetrized product \prod_{k=1}^N \psi_k(\mathbf{r}_k) yields a fully antisymmetric state, vanishing if any two orbitals are identical due to the Pauli principle. For bosons, the symmetrizer replaces (-1)^p with +1. These projectors ensure wavefunctions transform correctly under exchanges, with eigenvalues \pm 1 distinguishing fermionic and bosonic statistics.^[10]^[11] An illustrative example is the ground state of the two-electron helium atom, where the total wavefunction must be antisymmetric under electron exchange. The unsymmetrized product is \phi_{1s}(\mathbf{r}_1) \phi_{1s}(\mathbf{r}_2) \otimes |\alpha \beta\rangle, with \phi_{1s} the hydrogenic 1s orbital and |\alpha \beta\rangle denoting spin-up and spin-down. The exchange operator \hat{P}_{12} maps this to \phi_{1s}(\mathbf{r}_2) \phi_{1s}(\mathbf{r}_1) \otimes |\beta \alpha\rangle. For the singlet spin state (antisymmetric: \frac{1}{\sqrt{2}} (|\alpha \beta\rangle - |\beta \alpha\rangle)), the spatial part is symmetrized as \phi_{1s}(\mathbf{r}_1) \phi_{1s}(\mathbf{r}_2) (already symmetric for identical orbitals), yielding the total antisymmetric ground state \frac{1}{\sqrt{2}} [\phi_{1s}(\mathbf{r}_1) \alpha(1) \phi_{1s}(\mathbf{r}_2) \beta(2) - \phi_{1s}(\mathbf{r}_1) \beta(1) \phi_{1s}(\mathbf{r}_2) \alpha(2)]. In contrast, for the triplet spin state (symmetric), the spatial part would be antisymmetrized, leading to an excited state with nodal structure that reduces electron-electron repulsion. This demonstrates how exchange enforces correlation, altering probability densities compared to symmetrized forms.^[10]

Properties and Eigenvalues

The exchange operator \hat{P}, which implements particle interchange in the Hilbert space of identical particles, is both unitary and Hermitian. This follows from its definition as a permutation operator, satisfying \hat{P}^\dagger = \hat{P}^{-1} = \hat{P} and \hat{P}^2 = \hat{I}, where \hat{I} is the identity operator. The unitarity ensures preservation of the inner product under particle exchange, reflecting the indistinguishability of identical particles, while the Hermitian property guarantees real eigenvalues. Consequently, the eigenvalues of \hat{P} are restricted to \pm 1.^[12] The spectral properties of the exchange operator are tied to the symmetry requirements of identical particles. For bosons, the eigenstates with eigenvalue +1 span the totally symmetric subspace, invariant under even permutations of particle labels. For fermions, the antisymmetric subspace corresponds to eigenvalue -1 under odd permutations (transpositions), with the overall sign determined by the parity of the permutation: +1 for even permutations and -1 for odd ones. In systems with N particles and M single-particle states (M > N), these eigenspaces exhibit degeneracies given by the dimensions of the symmetric and antisymmetric representations of the permutation group S_N, such as \binom{M+N-1}{N} for the bosonic case and \binom{M}{N} for the fermionic case in higher-dimensional orbital spaces. These degeneracies highlight the group-theoretic structure underlying the operator's action.^[13]^[14] The exchange operator commutes with the Hamiltonian for systems of identical particles, [\hat{P}, \hat{H}] = 0, provided the Hamiltonian is symmetric under particle relabeling, as is required by the fundamental principles of quantum mechanics for indistinguishable particles. This commutation relation ensures that the total wavefunction can be chosen as simultaneous eigenstates of \hat{H} and \hat{P}, conserving exchange symmetry during time evolution and enabling the classification of states into bosonic or fermionic sectors. In the second-quantization formalism, the exchange operator for swapping occupations between single-particle orbitals i and j is represented using creation and annihilation operators. For fermions, it takes the form \hat{P}_{ij} = a_i^\dagger a_j a_j^\dagger a_i, incorporating anticommutation relations that introduce sign factors to enforce antisymmetry; this operator acts on Fock states by interchanging particle labels while preserving the overall fermionic statistics.^[15]

Role in Many-Body Theory

In Hartree-Fock Approximation

In the Hartree-Fock approximation, the exchange operator corrects for the classical Coulomb repulsion in the effective one-electron potential by accounting for the indistinguishability of electrons through antisymmetrization of the wavefunction. The many-electron wavefunction is constructed as a Slater determinant of orthonormal spin-orbitals to enforce antisymmetry under particle exchange, given by

\Psi = \frac{1}{\sqrt{N!}} \det\left[\phi_i(\mathbf{r}_j)\right],

where N is the number of electrons and \phi_i are the molecular orbitals. This form ensures that the expectation value of the Hamiltonian incorporates exchange effects from the two-electron integrals involving permutations of electron coordinates.^[16] The derivation of the exchange term in the Fock operator proceeds from the variational minimization of the energy for this Slater determinant wavefunction, leading to a non-local operator that modifies the Hartree potential.^[16] Specifically, the exchange operator \hat{K}_k associated with an occupied orbital k acts on an orbital \phi_j(\mathbf{r}) as

\hat{K}_k \phi_j(\mathbf{r}) = -\left[ \int \frac{\phi_k^*(\mathbf{r}') \phi_j(\mathbf{r}')}{|\mathbf{r} - \mathbf{r}'|} \, d\mathbf{r}' \right] \phi_k(\mathbf{r}),

where the total exchange operator is \hat{K} = \sum_k \hat{K}_k with the sum over occupied orbitals k, representing the correction to the electron-electron repulsion due to quantum exchange. This term arises from the antisymmetric two-electron integrals in the energy expression, effectively reducing the repulsion for electrons of the same spin.^[17] In the Hartree-Fock equations, the exchange operator contributes to the self-consistent Fock operator, yielding

(\hat{h} + \hat{J} - \hat{K}) \phi_i = \epsilon_i \phi_i,

where \hat{h} is the one-electron core Hamiltonian, \hat{J} is the Coulomb operator, and \hat{K} is the sum of exchange operators over occupied orbitals.^[16] The orbitals \phi_i are determined iteratively until self-consistency is achieved, with the exchange ensuring the correct fermionic statistics. Exact exchange is incorporated in the restricted Hartree-Fock method, where spatial orbitals are doubly occupied with opposite spins, maintaining spin-restricted symmetry.^[16] In unrestricted Hartree-Fock, separate spatial orbitals for alpha and beta spins allow for spin polarization but introduce approximations, such as potential spin contamination, as the exchange is computed using spin-dependent densities without enforcing pure spin states.

In Density Functional Theory

In density functional theory (DFT), the exchange operator from wavefunction-based methods is approximated through functionals of the electron density \rho(\mathbf{r}), enabling computationally efficient treatment of exchange effects in many-electron systems. The Kohn-Sham formulation maps the interacting system onto a non-interacting reference with the same density, where the exchange-correlation energy E_{xc}[\rho] encapsulates exchange and correlation via an unknown functional. The exchange component E_x[\rho] arises from the Pauli exclusion principle and is approximated in the local density approximation (LDA) by integrating the exchange energy per particle of a uniform electron gas over local densities. This yields the explicit form

E_x^{\text{LDA}}[\rho] = -\frac{3}{4} \left( \frac{3}{\pi} \right)^{1/3} \int \rho^{4/3}(\mathbf{r}) \, d\mathbf{r},

derived from the exact exchange energy for the homogeneous electron gas, where the prefactor ensures dimensional consistency and scaling with density. The corresponding exchange potential, which enters the Kohn-Sham equations as the functional derivative v_x(\mathbf{r}) = \frac{\delta E_x[\rho]}{\delta \rho(\mathbf{r})}, is obtained by varying the LDA functional with respect to \rho. For the uniform electron gas model, this derivative simplifies to v_x(\mathbf{r}) = -\left( \frac{3}{\pi} \right)^{1/3} \rho^{1/3}(\mathbf{r}), known as the Slater exchange potential after its approximation in atomic calculations, though originally rooted in the Dirac expression for free-electron exchange. This local potential captures the average exchange field but overestimates the exact Hartree-Fock exchange by a factor of $3/2 in the uniform limit, reflecting its semi-empirical nature for inhomogeneous systems. To improve upon pure LDA exchange, which underestimates band gaps and delocalization errors, hybrid functionals incorporate a portion of exact Hartree-Fock exchange, which depends on orbitals rather than density alone. A prominent example is the B3LYP functional, where 20% of the exchange is from exact Hartree-Fock, combined with 80% local spin density (LSD) exchange plus a gradient correction from Becke 1988, and correlation from Lee-Yang-Parr plus Vosko-Wilk-Nusair local correlation. Specifically,

E_{xc}^{\text{B3LYP}} = 0.20 E_x^{\text{HF}} + 0.80 E_x^{\text{LSD}} + 0.72 \Delta E_x^{\text{B88}} + 0.19 E_c^{\text{VWN}} + 0.81 E_c^{\text{LYP}}.

This admixture enhances accuracy for thermochemistry and excitation energies by partially restoring the nonlocal character of exact exchange while retaining DFT's efficiency. Compared to pure Hartree-Fock, which treats exchange exactly but neglects electron correlation, DFT approximations like LDA and hybrids better account for correlation effects through the E_c[\rho] term, leading to improved binding energies and structural predictions in diverse systems. However, the density-based exchange hole in these functionals remains approximate, often failing to satisfy exact constraints like the adiabatic connection, which limits precision in strongly correlated regimes.^[18]

Applications

In Quantum Chemistry

In ab initio quantum chemistry methods, the exchange operator plays a crucial role in accurately describing molecular binding energies by incorporating the antisymmetry requirements of the electronic wavefunction, which prevents unphysical behaviors in bond dissociation processes. For instance, in the unrestricted Hartree-Fock (UHF) treatment of the H₂ molecule, the exchange contribution enables a dissociation limit close to that of two hydrogen atoms with a total energy of -1 Hartree, addressing the artificial attraction that arises in the exchange-free Hartree method due to uncompensated self-interaction of electrons with the same spin, whereas restricted HF fails to dissociate properly.^[19] This exchange effect is particularly evident along the H₂ dissociation curve, where it stabilizes the proper separation of electron densities between the nuclei, yielding a binding energy close to the experimental value when combined with correlation corrections.^[20] Computationally, evaluating the exchange operator in HF theory involves calculating two-electron exchange integrals over Gaussian basis sets, which traditionally scale as O(N⁴) with the number of basis functions N due to the need to sum over pairwise electron interactions. To mitigate this bottleneck for larger molecules, techniques such as the resolution-of-the-identity (RI) approximation, also known as density fitting, are employed to approximate the exchange matrix elements by projecting onto an auxiliary basis set, reducing the scaling to nearly O(N³) while maintaining high accuracy for exchange energies within 1 kcal/mol.^[21] These implementations are standard in quantum chemistry software and enable practical HF calculations for systems with hundreds of atoms.^[22] The exchange operator also significantly influences computed molecular properties such as ionization potentials (IPs) and excitation energies by modulating orbital energies and response functions. In HF theory, Koopmans' theorem approximates IPs as the negative of the highest occupied molecular orbital energy, where the exchange term contributes to the correct ordering and magnitude, often within 1-1.5 eV of experiment for small molecules like water.^[23] For excitation energies, time-dependent Hartree-Fock (TDHF) incorporates exchange in the response equations, capturing local excitations accurately; for example, in ethylene, TDHF predicts the π→π* transition at about 7.8 eV, closely matching coupled-cluster benchmarks, with exchange ensuring proper treatment of electron-hole interactions.^[24] A notable application is in predicting ferromagnetism in organic radicals using unrestricted Hartree-Fock (UHF), where the exchange operator induces spin splitting in the molecular orbitals, favoring high-spin ground states. In systems like nitroxide-based diradicals, UHF exchange splitting between α and β orbitals stabilizes ferromagnetic alignment with exchange coupling constants J up to 100 cm⁻¹, as demonstrated in meta-phenylene-linked radicals, guiding the design of organic magnets.^[25] This approach highlights exchange's role in capturing intramolecular spin interactions without explicit correlation.^[26]

In Condensed Matter Physics

In condensed matter physics, the exchange operator plays a crucial role in describing electron interactions in solid-state systems, particularly through tight-binding models that capture lattice effects and collective behaviors. In the Hubbard model, which models strongly correlated electrons on a lattice, the exchange interaction arises in the large on-site repulsion limit U \gg t, where t is the hopping amplitude. The effective low-energy Hamiltonian includes an antiferromagnetic superexchange term J \sum_{\langle i,j \rangle} \mathbf{S}_i \cdot \mathbf{S}_j, with J = 4t^2 / U, derived from second-order perturbation theory involving virtual hopping processes between neighboring sites that mediate spin alignment without net charge transfer. This term stabilizes magnetic order in half-filled systems, highlighting how the exchange operator enforces fermionic antisymmetry to favor antiferromagnetism over direct Coulomb repulsion. The exchange operator also influences band structure calculations in density functional theory (DFT) for periodic solids. In the local density approximation (LDA), the approximate exchange potential often underestimates band gaps in semiconductors and insulators by 30-50%, as it inadequately captures the nonlocal nature of exact exchange, leading to delocalized orbitals and reduced excitation energies.^[27] Corrections via the GW approximation, which incorporates exact exchange and correlation through the screened Coulomb interaction in the self-energy, yield quasiparticle band gaps much closer to experiment, improving predictions for optical properties and transport in materials like silicon and gallium arsenide.^[28] In magnetic applications, the exchange operator drives itinerant ferromagnetism in metals via band splitting. The Stoner criterion determines the instability of the paramagnetic state, requiring the product of the density of states at the Fermi level N(E_F) and the Stoner parameter I (derived from the exchange integral) to exceed 1, i.e., I N(E_F) > 1.^[29] This leads to an exchange splitting \Delta = I \mu, where \mu is the spin polarization per electron, shifting majority and minority spin bands and lowering the total energy through partial band filling. In transition metals like iron, this mechanism explains Curie temperatures around 1000 K without localized moments. Exchange effects are particularly evident in transition metal oxides, where strong correlations beyond mean-field approximations explain Mott insulating behavior. In compounds like NiO or MnO, the half-filled d-shells lead to a Mott gap due to on-site Hund's exchange and Coulomb repulsion, but simple mean-field treatments overestimate metallic character; dynamical fluctuations and multiplet effects, captured in cluster extensions of the exchange operator, reveal charge-transfer insulation and antiferromagnetic order with Néel temperatures up to 500 K.^[30]^[31]

References

[1]
9.2: The exchange operator and Pauli's exclusion principle
Oct 10, 2020 · We introduce the exchange operator P ^ 12 : an operator which permutes the labels of the particles. This is a rather strange operator, because ...
[2]
[PDF] exchange operator formalism for an infinite family of solvable ... - arXiv
Jan 12, 2010 · The exchange operator formalism in polar coordinates, previously consid- ered for the Calogero-Marchioro-Wolfes problem, is generalized to a ...<|control11|><|separator|>
[3]
Exchange Operator: Physics Fundamentals & Quantum Example
Nov 1, 2023 · The Exchange Operator determines the magnetic properties of materials in Solid State Physics. It governs the exchange interaction between electrons in a ...
[4]
Chapter 12: Identical Particles - ESM Intranet Site
Chapter 12: Identical Particles . Note. Quantum mechanics is like Belgian endives: it is an acquired taste. - ... The exchange operator is defined as: \hat{P}_{12} ...
[5]
[PDF] Identical Particles 1 Two-Particle Systems - Physics Courses
we define the exchange operator Pij = Pji which exchanges the coordinates of ... Kemble, The Fundamental Principles of Quantum Mechanics). Such a set of ...
[6]
The development of the concept of exchange forces in the 1930s
Jun 20, 2024 · The onset and the development of the concept of exchange force in quantum physics are historically reconstructed, starting from Heisenberg's
[7]
On the theory of quantum mechanics - Journals
On the theory of quantum mechanics. Paul Adrien Maurice Dirac. Google ... Published:01 October 1926https://doi.org/10.1098/rspa.1926.0133. Abstract. The ...
[8]
Blurred orbits and blurred particles: Heisenberg's 1926 helium atom
Apr 5, 2025 · Although the indistinguishability of the electrons and indeterminacy are common explanations for the blurring of electron orbits, we argue that ...Missing: identical | Show results with:identical
[9]
[PDF] Chapter 8 - Identical Particles - MIT OpenCourseWare
May 8, 2022 · A permutation is said to be even if it is the product of an even number of transpositions, and it is said to be odd if it is the product of an ...
[10]
[PDF] Identical Particles
The symmetrization postulate applies to exchange of any pair of identical particles of any species. We have only defined the exchange operator in these notes.
[11]
[PDF] Introductory Quantum Chemistry Chem 570a: Lecture Notes Prof ...
Hint: Use the integral form of Dirac's delta function: δ(p − pj) = 1. 2πh. R ... X1(r1) is defined as the exchange operator,. ˆ. X1(r1) = n. X k6=j hχ0 k(2)|.
[12]
[PDF] Systems of Identical Particles - CMU Quantum Theory Group
Mar 21, 2011 · The permutation operators form a group under multiplication which is isomorphic to the group of permutations under composition. 1.5 Symmetric ...
[13]
Particle exchange statistics beyond fermions and bosons - Nature
Jan 8, 2025 · It is commonly believed that there are only two types of particle exchange statistics in quantum mechanics, fermions and bosons, ...
[14]
[PDF] arXiv:quant-ph/0003118v1 24 Mar 2000
From the properties of the exchange operators ˆP(j,k) it follows that the permutation operators admit only two common eigenstates, with the eigenvalues ǫj,k ...
[15]
[PDF] arXiv:2307.01963v3 [quant-ph] 2 Jan 2024
Jan 2, 2024 · We are concerned with continuous-time quantum walks (CTQW) of identical particles [43–49] and ... It acts as an exchange operator on the 1-fermion ...
[16]
https://doi.org/10.1103/RevModPhys.23.69
[17]
Perspective: Fifty years of density-functional theory in chemical physics
Apr 1, 2014 · EX is the exchange energy of the Slater determinant of the Kohn-Sham orbitals, and EC is everything else. Because the correlation hole ...
[18]
[PDF] Describing static correlation in bond dissociation by Kohn–Sham ...
Static correlation, a left-right correlation, is important in bond dissociation. Standard DFT methods underestimate this, and exchange functionals can mimic it.
[19]
Nonempirical Adiabatic Connection Correlation Functional from ...
Mar 26, 2025 · The dissociation curve of H2 within a spin-restricted formalism ... (GGAs) for exchange and correlation with Hartree-Fock (HF) exchange ...
[20]
Resolution-of-the-identity approximation for complex-scaled basis ...
Sep 18, 2019 · ... Hermitian RI-HF and RI-MP2 methods. In RI-HF, the Coulomb and exchange contributions to an element Fμν of the Fock matrix are approximated as.
[21]
RI-MP2: optimized auxiliary basis sets and demonstration of efficiency
Efficient, approximate and parallel Hartree-Fock and hybrid DFT calculations. A 'chain-of-spheres' algorithm for the Hartree-Fock exchange. 2009, Chemical ...
[22]
Influence of the exchange-correlation potential in methods based on ...
Oct 24, 2013 · Accurate exchange-correlation potentials are found to be essential for getting accurate energies. Methods employing in the Kohn-Sham self-consistency process
[23]
[PDF] Excited states from time-dependent Hartree-Fock and density ...
Feb 9, 2015 · A fully numerical method for the time-dependent Hartree-Fock and density functional theory (TD-HF/DFT) with the Tamm-.
[24]
Effect of Hartree-Fock exact exchange on intramolecular magnetic ...
Jan 13, 2015 · Among them, organic diradicals are the simplest magnetic system containing only two magnetic centers, which are suitable systems to investigate ...
[25]
High-Spin S = 2 Ground State Aminyl Tetraradicals - ACS Publications
The quintet ground state with this ΔETQ corresponds to a ferromagnetic exchange coupling within the tetraradical that is more than 3 orders of magnitude ...Epr Spectroscopy · Dimers Of S = 2... · Decay Kinetics Of Aminyl...
[26]
LDA, GW, and exact-exchange Kohn-Sham scheme calculations of ...
Nov 29, 2001 · The GW approximation is applied perturbatively either on top of the LDA, or EXX band structures in the zero order. It is argued that such a ...
[27]
Combining GW calculations with exact-exchange density-functional ...
Feb 16, 2005 · Combining GW calculations with exact-exchange density-functional theory: An analysis of valence-band photoemission for compound semiconductors.
[28]
Collective electron ferromagnetism | Proceedings of the Royal ...
The advantages of a collective electron treatment for ferromagnetism were pointed out some years ago in a paper (Stoner 1933) in which it was shown that such a ...
[29]
Another mechanism for the insulator-metal transition observed in ...
Apr 10, 2008 · Mott 1 proposed the insulator model for transition metal oxides with partially filled d band. Combined with the Hubbard theory, this model ...
[30]
Doping a Mott insulator: Physics of high-temperature superconductivity
Jan 6, 2006 · Therefore we have to go beyond the mean-field theory and take into account the fluctuation around it. In other words, the local gauge ...